Patent GB-911172-A (GB)
Title: Improvements in treatment of sulfide minerals
IPC: C22B3/08
Filed: 1959-01-12
Abstract: Sulphide minerals containing iron and non-ferrous metals having an atomic ratio of sulphur to iron in excess of unity are treated to recover the contained sulphur, iron and non-ferrous metal values therefrom by removing excess labile sulphur, if present, by heating to a temperature a little below the melting-point of ferrous sulphide, adding iron in an amount in excess of that sulphur associated with the iron which is in excess of an atomic ratio of sulphur to iron of unity, and heating at a temperature below the melting-point of ferrous sulphide for a period sufficiently long to reduce the atomic ratio to less than unity and render the contained iron sulphide soluble in dilute mineral acid.  The heating to remove sulphur may be effected in the presence of neutral, reducing or oxidizing gases and at reduced, atmospheric or elevated pressures. Where the reducing gas contains hydrogen, the sulphur is removed as H2S, and where the oxidizing gas contains oxygen, as SO2.  In the latter case, a small amount of the ferrous sulphide may be oxidized to a hydrogen-reducible iron oxide, and the sulphur dioxide may be converted to H2SO4.  The lebile sulphur may be removed at a temperature between 600 DEG -800 DEG C., and even as low as 450 DEG C. The iron may be added as metallic (including sponge) iron or as iron oxide or other hydrogen-reducible iron compound.  The iron or iron oxide may be added either to the original sulphide feed, if low in labile sulphur, or to the mineral from which labile sulphur has been removed.  When iron oxide is used, the mineral is treated with a reducing gas.  The calcine is treated with dilute H2SO4 to evolve H2S, the calcine being in slight excess, and to provide a neutral solution of ferrous sulphate, and the residue, possibly containing the sulphides of copper, lead, gold, silver, nickel, cobalt and zinc and also silica is treated with excess dilute H2SO4 to evolve more H2S and to provide an acid solution of iron and zinc sulphates. Treatment of this solution with a calcine containing only zinc and iron sulphides precipitates zinc sulphide leaving a neutral solution of ferrous sulphate, which may be heated at 450 DEG F. in the presence of oxygen and of a small amount of CuSO4 as catalyst to precipitate hydrated ferric oxide, used as a source of iron, and to leave dilute sulphuric acid, which is recycled. Alternatively, the ferrous sulphate may be recovered by evaporation and heated with pyrities in the presence of osygen to provide ferric oxide and sulphur dioxide.  In Example 1, a sulphide mineral is oxidized with air at 700 DEG -900 DEG C. until 30% of the sulphur is removed as SO2, and the still hot mixture treated in a furnace at 700 DEG C. with a hydrogen-containing gas for 10-15 minutes.  The calcine is leached in excess 10% sulphuric acid solution and the evolved H2S collected, and the leach solution filtered and neutralized with excess calcine to provide a neutral ferrous sulphate solution, which is processed to recover iron oxide.  The copper residue remaining after leaching is processed to metal by conventional processes, and the released SO2 combined with the H2S evolved during leaching to produce sulphur.  In Example 2, the excess sulphur is recovered as H2S by roasting in the presence of generator gas containing 50% hydrogen, and Fe2O3 recycled from the iron plant was added to the hot mixture which is then further heated in the presence of hydrogen. The mixture is agitated with an acid solution from copper oxide leaching to precipitate the copper as CuS.  The ferrous sulphate solution is mixed with pyrites concentrate, and the mixture evaporated and roasted to provide Fe2O3 and a SO2-containing gas.  In Example 3, the recovery of copper, nickel and cobalt as sulphides by suitable H2S treatment is referred to.  In Example 4, the initial iron is added as ferrous sulphate to one half of the mineral mixture oxidatively roasted, while the other half is heated without iron addition in the presence of hydrogen, and the mixed calcines are heated in the presence of hydrogen.  Treatments to recover lead, copper, and precious metals and zinc sulphide are described.  The recovery of gold, silver, tin, mercury, antimony and selenium is also referred to.